Process for preparing polyvinyl acetal resins



Patented Nov. 9, 1943 H I assignors to Eastman Kodak Company, Boohester, N. -Y.,- a 'oorporation of New Jersey No Drawing." Application June a,

SerialNo.339,529

This invention relates to a process forIpreparing resins and more particularly toa process for preparingpolyvinyl acetal, resins.

It is known that polyvinyllacetal resins a. be

prepared by. concomitantly deesterifyingpoly vinyl esters and condensing the -,deesterified product with aldehydes, inthe presenceof a] catalyst. It is iurther known" that polyvinyl esters can be first partially deesterified and ;that= the partially deesterifiedlester can then be .fur:

In either of the aforesaid v generall types a processes, deesterlfication has beenaccomplished in alcoholic and in organic acid media. Qurimmovements relate acidmedia. v r

In the preparation of r from polyvinyl esters by anyprocess, the prob lem is toproduce' resinslow in hydroxyl-and ester. group content, which are as free from colored;

to deesterifioation inorganic as well as'uncoloredside reaction products. as. possible. Toattainthis end, it has been -pro-; posed to react polyvinyl esters and aldehydes in the presence ofalcohols at. temperaturesof about 40'? C. in the presence of small amounts oi :acid catalysts. Such processes, while fairly satisfactory for certain aldehydes, are quite unsatisia c tory for a number, e. g., formaldehyde. Formaldehyde and certain other aldehydesqreactsoslowly under such .conditionsthat it is actually plicalole' to aldehydes comprises reacting polyvinyi esters and aldehydes in the. presence of Y aqueous acetic acid anda catalyst at about 50 C.

impossible to obtain resins low inhydroxyl group content; A process whichis moregenerally ap- Such processes have the disadvantage of requiring a verylong time for completion (i. e., to attain low ester group content)--at best around eight'days. unless a large amount oI-catalyst is employed. The resins obtained by. .such processes, while of good quality, sufierd'rom having remained incontact with the catalyst. acid. for so long a time. whereby side reactions can talre place to a greater or lesser extent. It isto improvement, of. such organic acid processes that. our efiorts have been directed. 7.

We set out toshorten the reaction time of the so-called organic acid processes without increasing temperature or concentration-of. catalyst;

an increase of either of which in the previously.

known processes has resulted in-undesirable polyvinyl resins (crate-173) required.

products. The robiem'w scom ncated =15 lth'e fact that in large scale productionpr; acetal resins. it isessential tohave homogeneous Q reaction mixtures in order that of, agitation 'of the reactantsfdurlng" the; process I #It is accordingly an obiecto ourginve'itio .tii. provide an improved process' ior the 'prepafr ti of polyvin'yl acetal resins. I t is a iirther objectj ofour invention to produce high quamyresms,

4 as free from side reaction products as possible" and in the shortest vtime possible. Other and more specific objects will appear hereinafter. According to our process, we 'h'ydrolyzeg inIthe.-

presence or a catalyst, a polyvinyl e strdissolved "in a' reaction mixture czoinprising; water.

and an organicacid'which miscible in flall -pro portions with water at about. 202 Q. During the hydrolysis ,idee'steriiicationi for the polyyinyl ester, we add wa er to the reaction mixture. The? amount of water added and'the rate at'. which it;' is added are limited only by the tendencyloi' polyvinyl ester; partially deesteriiied or otherwise, to precipitate or separate irom thetrea'c tion mixture. It is advantageous to avoid any precipitation of polyvinyl ester,',partially dees teriiled or' otherwise. After the polyvinyl ester is appreciably hydrolyzed, we 'add aldehyde to the reaction mixture and increase the amount of organic acid in, the reaction mixture at arater which substantially precludes precipitation of rapidly. either before or simuita'neously with theadditicn oi the aldehyde.

:While', according to our'proces s. the aldehyde can be added'to the reaction mixture at anytime after the 'polyviriyl ester has been hydrolyzed'to I an appreciable extent, e g.,'fafter' the polyvinyl ester has been hydrolyzed to 'theextent of 5% or 10%, it is advantageous to carryout the .hydrolysis to a much greatervextentj be oreaiidihg the aldehyde. Most advantageously, the poly vinyl ester is hydrolyzed at leastto the point vwhere 'it is water-soluble before addin'g any aldehyde. V

While our improved process is subject 'to 'variation, the following example will serve to illustrate the mannerflof practicing. ourinven'tion; These examples are not intended to limit the scope of our invention. In the following .examples, theviscosityof the. polyvinyl ester stated isthat of its molar solution (86.05 g. per liter, in. the case of polyvinyl acetatei in benzene at about20 C.' v i .acid (sp. .g. 1.84) were added. mixture was-heated at 75 C. with agitation. .220

2 I i L Example :1

100 :-par ts o'i -.pO vin yl acetate (viscosity '25) weredissolved in 150,,parts of glacialacetic acid and 100 parts of .water. parts of sulfuric The resulting partsohwater were added to thereaction.mixture gradually over a period of-about eignthours while maintaining the temperature at about 7 75 .C. Attheend of this -time. the.mixture was agitatedand heated at 75 C. for a further 12 hours. At the end of time the hydrolysis product had become water soluble, as evidenced by theiact that .a testportion oftthereaction I mixture was completely miscible with threetimes itsiown volumeoi-water. The temperature of the reaction mixture was lowered to about 40 C. .330-pa'rts of glacial acetic acid and 50 parts of paraldehyde were added to the reaction mixture with stirring, in order to insure complete The resulting mixture was allowed to stand about five days. At the end of this time,

Example 2 100 parts :of polyvinyl acetate (viscosity were dissolved in 150 :parts of glacial acetic acid andlOO partsofswater. 10 partsof sulfuric acid 5 -(sp.-g. 1.84) .wereadded. .Theresulting mixture was heated at 75C. with agitation. 220 parts :of water were added to the reaction mixture gradually overv a period not about eight "hours while maintainingthe temperature at about 75 0. Atthe end of this time; ithe mixture was agitated and heated .at 575 C. for .aiurther 12 :hours. At the end of this time the hydrolysis product 'hadbecome water soluble, as evidenced by the fact that a test portion of the reaction mixture was completely miscible withjthree times its own volume of .water. The temperature of the reaction mixture was lowered to about 40 C. 100 .parts' of a 50%. (byjweight) solution of acetaldehyde in glacial acetic acid were added to thereactionmixture with stirring. :280 parts of glacial acetic acid werealso added to the reaction mixture. The resulting mixture was .allowed to'st and at about 40 C ior-about5 days. At the end of this time, .the reaction mixture :was :poured slowlyinto water to precipitate-the resin, The precipitated resin was thoroughly washed with water andthen dried. The resin contained an acetate group content equivalent to about 10% by weight of polyvinyl'acetate and a hydroxyl group contentequivalent to .about:8% by weight of polyvinyl alcohol. Thenresin was pure white in color.

In practicing our invention, any po v yl ester can be employed. Advantageously, apolyvinyl aliphatic.organicvester is employed. Most advantageously, polyvinyl acetate is used as a V starting-material. Polyvinyl acetate is also probably the cheapest and most readilyavailable polyvinyl ester. Polyvinyl acetate-propionate,

polyvinyl chloracetate, polyvinyl butyrat and polyvinyloleate-acetate'are examples of other polyvinyl esters which are-easily adapted to our new process. Polyvinyl esters of all viscosities can be employed. Poly-vinyl acetate-of .viscosities 15 :to160 are-advantageously employed.

The organi'c-acid-employed in the reaction mixture should be miscible .in all proportions "with water at about 20 C. Acetic'acid .is advan- 'tageously employed, although .mono-chloracetic acidpformic'acid and propionicacid are easily adapted to our process.

.Advantageousiy, the ratio of organic acid to water .in ithe" reaction .mixture at the beginning 02 tthe hydrolysis :of :the :polyvinyl ester is such that :theweightof i the organic sa'cid is more than .ithe weight offgthezwater. Most -advantageously, .atthelstart q thehydrolysis, the weight of the :organic .aci'djconstitutes from about-.60 to about 80% of .the lweight'of :the organic acid and water. m

'The 'ratio',, I 'ganicacid (organic acidplus water) to polyvinyl ester-in the reaction mixture at-the beginning of %.the hydrolysis is advantageously within therange about 1651 :to about 10:1, although ratios outside'zthispreferred range can*"be-'employ'ed.

hydrolysis' isadvantageously at leastabout'lO 0., I

a temperature within the frame "from about 7.0" C. to about 0. being preferable. Upon addition aotth'e aldehyde; the temperatureis advantageously freduced to V at least about-50" 0.,

a temperature within :the range from "about" 20 C. .to about 50 C. being zpreferable. A temperature oi' about .40? C. is'lthemostadvantageous temperature to employ =during :the aldehyde reaction. f v

Cataly'sts ioi reactions ofthistype .are'very well known in the 'art. It is most advantageou to employ acid catalyst, particularly'mineral acid catalysts; such as hydrochloric or sulfuric acidfor example lnournew process, Acid catalysts, :pa-rticularly those Iminera'l acid catalysts given above; accelerate the initial hydrolysis very well and also accelerate the subsequent concomitant hydrolysis. and acetal condensation very' well. Either catalysts which can-,be employed are iorexample tric'hlor'acetic acid, organic sul- Ionic acids-andzinc chloride. zinc chloride accelerates-acetal condensations much better than itaccelerates hydrolysis in our n'ew process and shouldmot be-employedwalone to accelerate initial hydrolysis.

The concentration of catalyst employed will vary according to its-nature'and the nature of,

the-polyvinyliester and aldehyde employed. Gen-'- -eralLv1jlarger concentrations of catalyst accelcrate our new process, particularly the initial hydrolysis; more" rapidly. However, 'largercon centrations of catalystare advantageouslyavoid ed- When carrying out our process with temperatures of"70 to 100 C. for the initial hydrolysisand temperatures of 20 to 50 C. for

the subsequent concomitant i'urther hydrolysis andaceta'l condensation-only very small amounts parts by weight of aqueous orto about ten times its weight of a mixture or a from about 60% to about 80% aqueous acetic acid, in the presence of an amount of an acid catalyst equal to from about 5 to about by weight of the polyvinyl acetate, gradually increasing the weight of water during hydrolysis while maintaining the temperature at from about 75 to about 100 C., until the concentration of the aqueous acetic acid is decreased to from about to about and after the polyvinyl acetate is hydrolyzed to the point where it is watersoluble, changing the temperature to from about 20 to about 0., adding aldehyde and increasing the weight of acetic acid at a rate which substantially precludes precipitation of any polyvinyl acetal resin.

2. A process for preparing a pure white polyvinyl acetal resi comprising hydrolyzing, at a temperature of from about 7 5 C. to about 100 C., a polyvinyl acetate dissolved in from about six to about ten times its weight of a mixture of from about to about aqueous acetic acid, in the presence of an amount of acid catalyst equal to from about 5 to about 15% by weight 01 the polyvinyl acetate, gradually increasing the weight of water during hydrolysis while maintaining the temperature at from about 75 to about 0., until the concentration of the aqueous acetic acid is decreased to from about 30% to about 40%, and after the polyvinyl acetate is hydrolyzed to the point where it is watersoluble, changing the temperature to from about 20 to about 50 C., adding acetaldehyde and increasing the weight of acetic acid at a rate which substantially precludes precipitation of any polyvinyl acetal resin,

CARL J. MALM. v MAR'I'II SALO. 

